Arylamine salts of anthraquinonesulphonic acids as printing aids



Patented Aug. 6, 1946 ARYLAMINE SALTS OF ANTHRAQUINONE- SULPHONIC ACIDS AS PRINTING AIDS Roy Herman Kienle and Chester Albert Amick,

Bound Brook, N. J assignors' to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing.

Application July 1, 1943,

Serial No. 493,137

6 Claims.

This invention relates to anew type of dyeing and printing" assistant, dye compositions containing these assistants and products printed therefrom.

Use of printing-color pastes containing dyes, particularly in printing operations using vat dyes,

is sufficiently well-known so that the procedure has become almost standardized. The actual color source may be either a dye paste or a dye powder. In addition to the real color, a dye paste usually contains agents to prevent drying-out, settling and/or freezing. Dye powders, not being subject to these difficulties, do not require these agents but they usually contain agents or are so processed as to promote dispersibility.

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a gum dispersion, to form a printing-color paste which is suitable for application. In the case of vat dyes, it is also necessary to add a reducing agent and usually an alkali. Because the color yield from printing-color pastes often decreases rapidly as the paste ages after being made up, these printing-color pastes are usually prepared by the fabric finishers just. before they are to be used.

The printing-color pastes, however compounded, are then applied to textile, paper or other fabric materials for decorative or protectivepurposes. The printed pieces are dried, aged in a steam ager, treated with an oxidizing agent, rinsed andv finally dried. Usually in processing textiles, the printed fabric also is soaped at or near the boil with about a 0.1% soap solution and again rinsedbefore the final drying operation.

In making up and applying printing-color pastes it has been found that a material suitable for use as a printing assistant is of advantage in obtaining maximum color yield. The exact way in which these materials act to produce an improved color yield inprinting is not entirely understood. It is with these printing aids or assistants that the present invention is particularly concerned.

Although printing. aid are desirable in the printing-color pastes, the exact point at which they are added may vary. Dye pastes may contain printing. aids as one. of their components and printing-color pastes made therefrom will obviously contain the printing assistant. Where a printing assistant is not present in the dye paste, it may be added at the time of making up the printing-color paste.

It is preferable, however, that the printing as sistant be incorporated in the actual dye paste. Their addition at the proper point in the manufacture of the paste is not only easier, but in addition they are thus generally more uniformly dispersed throughout a printing-color paste made therefrom. As a result, the printing assistants usually operate more effectively when the printing-color paste is finally applied to the fabric.

It is only relatively recently that dye powders suitable for use in making up printing-color pastes have been available. Most of the printing aids previously used in dye pastes, being either liquid in form or extremely hydroscopic, can not be used with dye powders, the latter being necessarily limited to the use of dry solids. Neverthe-. less, it i desirable that printing assistants be incorporated in the powders at the time of manufacture for the same reasons which apply in the case of dye pastes.

Dye pastes containing, various liquid printing assistants have been made. Among the liquid materials used are the alkylol amines, for example, triethanol amine; and/or polyhydric alcohols such a glycerine, glycol, diethylene. glycol and the like. Various derivative-s therefrom also have been tried. If a printing aid is to be incorporated in a dye powder, a solid printing aid is necessary. Examples of such solids which have been used in the past include the hydrochlorides of alkylol amines; silver salt (sodium anthraquinone beta-sulfonate); anthraquinone and certain metal salts such as those of cobalt and iron.

Unfortunately, most of these printing aids previously used are not as satisfactory as may be desired. Many of them will not in all cases produce the intensification of color for which they are intended. Others, such a the polyhydric alcohols, cause deterioration of the printing-color pastes so'that marked variations in the strength of prints therefrom are observable even after the printing-color paste has been allowed to stand for only a relatively short time. Many of them are satisfactory with some colors but have an adverse eifect on others, even to the extent of visibly altering the shade. None of them are suittable without modification for use both in paste and powder compositions.

There remains, therefore, a demand for suitable printing assistants which will produce a satisfactory color intensification and will not cause deterioration of the dyeing or printing composition on standing. Preferably also, the assistants should be useful both with dye pastes and dye powders and in addition should be readily available or cheaply and easily prepared. It is, therefore, the object of the present invention to 3 provide a new type of printing assistant which possesses these desirable properties.

In general the objects of the present invention are accomplished by using a a printing assistant an arylamine salt of a quinone-sulphonic acid having the general formula forth in our copending application for United States Letters Patent, Serial No. 493,133 filed of even date.

So far as the salts of the present invention are concerned, Ar of the generic formula may represent substantially any aryl or alkaryl radical. Excellent printing assistants are formed, for example when Ar represents such radicals as phenyl, naphthyl, tolyl, xylyl and the like radicals.

In the past quinone-sulphonic acids, such as 2 anthraquinone-sulphonic acid, and metal salts thereof have been used with vat dyes as printing assistants. It was found that these worked very well and they have been quite widely used. The arylamine salts, differ appreciably in structure since they are true addition salts whereas the formation of the soluble metal salts requires the condensation of a molecule of water.

In fact, the structure differs sufficiently so that salts such as those of the present invention were thought by the prior art to be too unstable for satisfactory use. Nevertheless, whatever the structure of the arylamine salts and the previ- CHaONHaS OaH So far as the present invention is concerned the assistants may be added to the printing-color pastes at any point. They may be incorporated into the thickener; into the dye pastes or powders or may be blended directly into the printing-color paste. However, as pointed out above, it is preferable that they be incorporated in the dye paste or powder during manufacture. If so desired they may be used with other printing assistants and other paste modifiers.

' The use of this new class of printing assistants possesses a number of important advantages. These compounds are dry solids, which may be readily powdered and blended in dye powders but are also soluble 0r dispersible in dye paste suspensions. They have, therefore a general appli-- cation in both dye pastes and dye powders. They do not cause deterioration of printing-color pastes on standing. They encourage the production of excellent color yields even under hot ageing conditions. Their use is simple since they may be employed as powders, as suspensions in water or alcohol.

In preparing the salts to be used as printing assistants according to the present invention, the quinonyl radical represented by Q in the generic formula is ordinarily alphaor beta-anthraquinone or betanaphthoquinone or a substituted derivative thereof. The corresponding derivatives of 1,4-napthoquinone do not appear to be capable of being isolated, if they form. In the case of beta-naphthoquinone, a: in the generic formula is ordinarily one since the salts of naphthoquinone-disulphonic acids are impractical to form.

Also, in preparing the salts to be used according to the present invention, a distinction must be made between the formation of these addition salts and the formation of the true sulphonamides which have a closely related structure. The sulphonamides which are formed by reacting a quinone-sulphonic acid with an arylamine under increased temperatures or by reacting an aryl-sulphanilyl compound with a quinone are not intended to be within the scope of the presentinvention. These compounds are specifically set ously-used metal salts and in spite of the belief of the art, the arylamine salts not only work well but are definitely superior when used as printing assistants. They invariably produce prints which are stronger and clearer than those which can be obtained from otherwise identical pastes in which either the corresponding acid or a metal salt thereof is used as the assistant.

While th dye and printing paste compositions of the present invention are not limited to use with dye paste or dye powder, they are primarily intended for use with thiO-indigo vat-dyes with which they are especially effective. Particularly good results may be obtained using the thio-indigo vat-dye powders of high autodispersibility set forth in Crossley et al., United States Reissue Patent 21,402, reissued March 9, 1940. By combining color materials of that patent into printingpaste compositions containing the printing assistants of the present invention, the full advantages of both may be gained with a resultant simplicity in use and excellence of shade and sharpness of color.

Printing pastes made in this way have the particular advantage that the dyes remain in a highly dispersed state as individual particles rather than as dispersions of particle aggregates. In the present specification and claims, where highlydispersed dyes are referred to, reference to pastes in which the dye particles are so dispersed is intended.

The invention will be more fully set forth in connection with the following examples which are intended to be illustrative and not by way of limitation. All parts are by weight unless otherwise noted.

In the succeeding examples, test prints were made on two different fabrics. When rayon is referred to, a titanium-dioxide-pigmented, all viscose-rayon fiat crepe was used. The cotton fabric referred to is an X80 bleached, unmercerized, cotton print-cloth. Ageing of the prints was carried out in a steam ager which was constructed in such a manner that controlled temperatures could be used. The temperature range normally used was -105 C. Those ageings referred to as plant or hot ageings were carried out in the temperature range of about 106110 C. In the case of the: cotton prints;- ageing periods of 3' minutes, 5 minutes or both were used. On rayon, ageing periods of 5 and minutes or both were used;- The shortestperiodwhich gives a satisfactory ageing is preferable.

Examplel A- paste wasprepared by slurrying 2,000 parts of 177. British (Stein Hall) in 5,000 parts of water and heating the mixture with continuous stirring until'the' temperature reached about 185 C Heating was continued for about 1 /2 hours after which 450 parts of powdered sodium carhon-ate and 450 parts-of powdered potassium ca bonate' were added and the mixture stirred until the carbonates dissolved. Heating was discontinued but stirring was continued until the temperature reachedapproximately 150 F. at which time 700 parts of sodium sulphoxylate formaldehyde were dissolved therein. Subsequently, 600

parts of glycerine were added and the paste bulked-to about 10,000 parts. Stirring was continued until the paste cooled to room temperature. In the succeeding examples this paste is referred to as thickener A.

Example 2' 2,100 parts of B2 British gum, 200 parts of tapioca flour and 500 parts of cornstarch were added" to 2,500parts of water and heated over a steam bathfor approximately 1 hours after the temperature reached about 185 F The source: of heat yvas then removed but stirring was continued until the temperature decreased. to

130 F. at which time 2,100 parts of potassium carbonate which had been previously dissolved in hot water was added to the cooked gum, 1,100 parts of sodium formaldehyde sulphoxylate were added to the: common mixture at a temperature of about 150 F. Subsequently, 1,400 parts of glycerine were added and after thorough stirring the whole was bulked to about 10,000 parts. The mixture waseooled and stirred continuously until the mass reached room temperature. In the succeeding examples this. mixture is referred to as thickener "B.

Example 3 720 parts of B-Z British gum and 720 parts of KAC-4 gum (Stein Hall) were added to 5,600 parts of water and heated over a steam bath for approximately 1 hours after the temperature reached about 185-l90 F. The source of heat was then removed but stirring was continued until the temperature decreased to 120 F. at which time, 1,200 parts of potassium carbonate which had been previously dissolved in 1,000 parts of water was added to the cooked gum. 1,560 parts of sodium sulphoxylate formaldehyde were dissolved in 1,500 parts of water at a temperature of about 140 F. and added to the common mixture with stirring until the whole was thoroughly mixed, 360 parts of glycerine were then added and after thorough stirring the whole was bulked to 12,000 parts. In the succeeding examples this mixture is referred to as thickener C.

Example 4 12 parts of a powdered aniline salt of anthra quinone-beta-sulphonic acid were added to 200 parts of a dispersed Vat Orange R powder (C. I.-l217), prepared according to U. S. Patent Reissue 21,402. This mixture was ball-milled for 5 hours after which time 66 parts of Cerelose were added and the milling wa continued for 18 hours. ;A second sample was prepared in the same way, using anthraquinone-beta-sulphonic acid. A third or control sample Was prepared as the two above except that no printing assistant was added, the Cerelose being increased to 78 parts in order'to maintain the color content equal. Five parts of each of the above products were mixed respectively with parts of thickener A and after thorough. mixing were printed on cotton. After drying in a hot air oven, the pieces were aged 3 and 5 minutes, respectively, in a steam ager. One set of prints was oxidized with K 1% sodium perborate solution at F. and asecond set with chrome and acetic acid at F. The printed pieces were then rinsed, soaped for five minutes at the boil with a 0.1 soap solution, again rinsed and finally ironed dry. Prints obtained from the pastes containing both printing assistants were stronger than those obtained from the paste containing Cerelose only. Further, those'made from the paste containing the aniline salt of anthraquinone-beta-sulphonic acid were noticeably stronger than that from the paste containing the anthraquinone-beta-su1phonic acid itself, Both methods of oxidation gave similar results.

Example 5 The pastes that were made'in Example 4- were allowed to stand for 24 hours and again were printed. The results were essentially the same as in Example 4.

Example 6 The procedure of Example 4 was repeated cept that printing thickener B was used in' place of thickener A. The prints were made on rayon. Again, both pastes containing the printing assistants were better than the control paste, those from the aniline-salt paste being both stronger and brighter than those from the sulphonic-ecid paste.

Example 7 900 parts of Vat Pink FF (66 di-chloro-A' dimethyl, 2,2 bis-thionaphthene indigo) presscake were defiocculated with sodium disulphodinaphthyl methane and passed through a Mikro colloidmill in order to give a smooth uniform suspension. This product was called Vat Pink FF defiocculated presscake. After determining the dye content of this material, a weighed amount was entered in a ball mill, To this mixture enough water was added to reduce the dye content to approximately 15% and the mix was ground for 24 hours. This 15% Pink FF water paste was called the blank. A second amount of Vat Pink FF defiocculated presscake containing approximately 30 parts of dye were entered in a ball mill and 6 part of the aniline salt of beta-anthraquinone-sulphonic acid Were added. Enough water was then added to reduce the dye content to approximately 15% and the mix was ground for approximatel 24 hours. This product was then analyzed for extracted solids and then tested against the blank using thickener A. The efiiciency factor was determined b comparing spectrophotometricall the color yield of the prints that were obtained against the percent of real dye present. The efiiciency factor is 1.68, indicating that the presence of the printing assistant improved the color yield approximately 68%.

Example 8 A sample of wet presscake of Vat Orange R (C. I.-121'l) was dispersed with sodium disulphadinaph-thylmethane and adjusted with water to contain about 12% real dye. 10 parts of this slurry were mixed with parts of a 6% suspension of the aniline salt of anthraquinone-betasulphonic acid, after which 85 parts of thickener C were added and the whole was intimately mixed. A second parts of the Orange R paste were likewise mixed with 5 parts of water and 85 parts of thickener C. Each of these pastes were printed on rayon and cotton. The prints obtained from the paste containing the aniline salt of anthraquinone-beta-su1phonic acid were much stronger and brighter than those obtained from the pastes containing water only.

Example 9 The procedure of Example 8 was repeated ex.

cept that the aniline salt of anthraquinone alpha-sulphonic acid was used. The results were essentially the same. The prints obtained from the paste containing the aniline salt of anthraquinone-alpha-sulphonic acid were better than those obtained from the paste containing water only.

Example 10 The procedure of Example 8 was repeated using the naphtholamine salts of both alphaand beta-anthraquinone-sulphonic acid. The results obtained when the printing assistant was present were essentially the same as in Example 8, in each case a markedly improved color yield being obtained.

Example 11 Example 10 was repeated except that the p-toluidine salts of the alphaand beta-anthraquinone-sulphonic acids were used. A blank with no assistant was also prepared. Each of these pastes were printed on rayon and cotton and those prints obtained from the paste containing the printing assistant were much stronger than those obtained from the paste containing water only.

Example 12 Again the procedure of Example 10 was repeated using the xylidine salts of alphaand beta-anthraquinone-sulphonic acid. The prints obtained from the paste containing the xylidine salts were in each case much stronger than those obtained from the paste containing water only.

We claim:

1. A color composition comprising a thio-indigo vat dye and an arylamine salt of a quinonesulphonic acid, the arylamine being a member selected from the group consisting of aniline, toluidine and xylidine and the quinone-sulphonic acid being a member selected from the group consisting of the monoand di-sulphonic acids of naphthoquinone and anthraquinone.

2. A color composition comprising a thio-indigo vat dye and an aniline salt of a quinonesulphonic acid selected from the group consisting of monoand di-sulphonic acids of naphthoquinone and anthraquinone.

3. A color composition comprising a thio-indigo vat dye and a toluidine salt of a quinonesulphonic acid selected from the group consisting of the monoand di-sulphonic acids of naphthoquinone and anthraquinone.

4. A color composition comprising a thio-indigo vat dye and a xylidine salt of a quinonesulphonic acid selected from the group consisting of the monoand di-sulphonic acids of naphthoquinone and anthraquinone.

5. A dye powder composition comprising a powdered thio-indigo vat dye and a dry powdered arylamine salt of a quinone-sulphonic acid, the arylamine being a member selected from the group consisting of aniline toluidine and xylidine and the quinone-sulphonic acid being a member selected from the group consisting of the monoand di-sulphonic acids of naphthoquinone and anthraquinone.

6. A printing paste composition comprising a thio-indigo vat dye, a thickener and an arylamine salt of a quinone-sulphonic acid, the arylamine being a member selected from the group consisting of aniline, toluidine and xylidine and the quinone-sulfonic acid being a member selected from the group consisting of the monoand di-sulphonic acids of naphthoquinone and anthraquinone.

ROY HERMAN KIENLE. CHESTER ALBERT AMICK. 

